Electrochemical Cells—What Electroanalytical Chemists Use

We can better understand the oxidizing or reducing tendencies of substances by studying electrochemical cells and electrode potentials. 

There are two kinds of electrochemical cells, voltaic (galvanic) and electrolytic. In voltaic cells, a chemical reaction spontaneously occurs to produce electrical energy. The lead storage battery and the ordinary flashlight battery are common examples of voltaic cells. In electrolytic cells, on the other hand, electrical energy is used to force a nonspontaneous chemical reaction to occur, that is, to go in the reverse direction it would in a voltaic cell. An example is the electrolysis of water. In both types of these cells, the electrode at which oxidation occurs is the anode, and that at which reduction occurs is the cathode. Voltaic cells wOl be of importance in our discussions in the next two chapters, dealing with potentiometry. Electrolytic cells are important in electrochemical methods such as voltammetry, in which electroactive substances like metal ions are reduced at an electrode to produce a measurable current by applying an appropriate potential to get the nonspontaneous reaction to occur (Cha]pter 15). The current that results from the forced electrolysis is proportional to the concentration of the electroactive substance. 

VOLTAIC CELL AND SPONTANEOUS REACTIONS—WHAT IS THE CELL POTENTIAL  

Consider the following redox reaction in a voltaic cell  

The released electrons flow through the wire to the other beaker where the Cef is reduced (at the cathode)  

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